KR101328097B1 - A color resist remover composition for tft-lcd preparation - Google Patents

Abstract

The present invention relates to a color resist stripping liquid composition for a TFT LCD to remove a color resist pattern and an overcoat in order to reuse a defective substrate generated during the color filter process of TF LCD. More specifically, (a) an inorganic alkali 1 to 50% by weight of a hydroxide compound selected from the group consisting of hydroxides, alkyl ammonium hydroxides having alkyl groups of 1 to 4 carbon atoms and phenylalkyl ammonium hydroxides, (b) sulfur compounds having a polarity of 5 to 30 % By weight, (c) 5 to 35% by weight alkylene glycol ethers having alkyl groups of 1 to 4 carbon atoms, (d) 2 to 30% by weight alkylene glycol dialkyl ethers having alkyl groups of 1 to 4 carbon atoms, (e) It relates to a peeling liquid composition for a color filter comprising 2 to 30% by weight of a water-soluble amine compound, and (f) a residual amount of water.

The color resist stripper composition of the present invention can remove the color resist and the overcoat in a short time, minimize the corrosion of the lower metal wiring, and in the subsequent rinsing process, organic solvents such as isopropyl alcohol and dimethyl sulfoxide Since there is an advantage that it can be rinsed with water only without the need for use, it is difficult to remove the conventional color resist pattern, thereby enabling reuse of the mostly discarded color filter substrate.

Color resist, overcoat, stripping solution, TF LCD

Description

Color resist stripper composition for TFT LCD {A COLOR RESIST REMOVER COMPOSITION FOR TFT-LCD PREPARATION}

The present invention relates to a color resist stripper composition for TFT-LCD, and more particularly, to remove a color resist and a color resist overcoat of a defective substrate generated during a color filter process, thereby removing a black mask. Or it relates to a color resist stripper composition for TFT LCD for reuse with a glass substrate.

The color filter substrate is composed of a color filter red cyan pattern and a black matrix, an overcoat, which is a protective film, and a common electrode for applying a voltage to the liquid crystal cell to block leakage light between each pixel and to improve contrast.

The process of manufacturing a color filter is as follows. First, Cr / CrOx or an organic material, which is used as a black matrix material, is coated on a glass substrate, and a pattern is formed on the glass substrate, depending on the use. After forming a black mask pattern, a color resist pattern for realizing color is formed by a photolithography technique. The color resist is applied onto a glass substrate and exposed to light to cure the color resist by photopolymerization. After the exposure is completed, the color resist is removed by undeveloped portions, and undergoes a calcination process.

The color resist is produced by a pigment dispersion method, a dyeing method, an electrodeposition method, etc. Among these, the pigment dispersion method is mainly used. Generally, organic pigments that implement color are dispersed in photopolymerization initiators, monomers, binders, and the like, which are photosensitive compositions such as photoresists. The photopolymerization initiator is a highly sensitive compound that receives light to generate radicals, and the monomers are bound to a polymer form after the polymerization reaction is initiated by the radicals, thereby becoming insoluble in the developing solvent. The binder protects the monomer in the liquid state from the developer at room temperature, and determines the stability of the pigment dispersion and the reliability of heat resistance, light resistance, chemical resistance, etc. of the red cyan pattern.

Defects generated in the current color filter process Once the color resist of the color filter substrate is cured, it is almost impossible to repair by removing only the wrong part of the pattern. Also, since the solvent that can remove the color resist is poor, the color filter is repaired. Most of them are disposed of immediately without rework.

The color resist has the characteristics of a negative resist. In general, the negative resist has a strong peeling performance because it is difficult to remove the peel compared with the positive type.

For this reason, conventionally, RIE (reactive ion etching) using an inorganic stripping solution and plasma was used. However, in the case of the inorganic stripping solution, the use of sulfuric acid, nitric acid, fuming sulfuric acid, a mixture of nitric acid and hydrogen peroxide heated to a high temperature of more than 120 ℃, not only adversely affects the safety of workers but also increases the risk of fire due to heating There has been discomfort that requires careful attention in handling. For example, a mixture of an alkyl benzene sulfonic acid and a non-halogenated aromatic hydrocarbon solvent having a boiling point of 150 ° C. or higher is disclosed in Japanese Patent Laid-Open No. 51-72503, and a mixture of alkyl aryl sulfonic acid, an aqueous aromatic sulfonic acid and a non-halogenated aromatic hydrocarbon solvent. In US Pat. No. 4,165,294, a stripper in which a polar or nonpolar organic solvent is added to eutectic acid and 1,2-dihydroxybenzene is disclosed in EP 0119337.

In addition, a method using reactive ion etching (RIE) using plasma, in which the etching of the cured color resist, which cannot be removed by general wet etching, is continuously removed using O2-RIE and SF6-RIE. 5,756,239, a cured color resist using polyester, polyamide, and noblock resin as an absorbent layer and a mixture of polysilane, polysiloxane, organosilicon compound, silica, and silicon nitride as the barrier layer, and the absorbent layer using oxygen. The method of using RIE using sulfur hexafluoride or nitrogen trifluoride as a barrier layer with plasma is disclosed in US Pat. No. 5,059,500. However, the etching of the color filter using the plasma requires high vacuum, high energy, difficult to set the process conditions, difficult to use in a large area, and has the disadvantages such as expensive equipment.

As described above, in the conventional color resist removal method, it is difficult to stably remove a large amount of color resist, there is a problem that the safety of workers, or productivity or yield is low.

Therefore, there is a need for a method of removing a large amount of color resist in a safe manner.

In order to solve the above problems of the prior art, an object of the present invention is to provide a stripper composition for safely removing a large amount of color resist and overcoat used during the color filter manufacturing process of TF LCD.

In order to achieve the above object, the present invention is (a) an hydroxide compound selected from the group consisting of inorganic alkali hydroxide, alkyl ammonium hydroxide having an alkyl group having 1 to 4 carbon atoms and phenylalkyl ammonium hydroxide 1 To 50% by weight, (b) 5 to 30% by weight of sulfur compound having polarity, (c) 5 to 35% by weight of alkylene glycol ether having alkyl group of 1 to 4 carbon atoms, (d) having an alkyl group of 1 to 4 carbon atoms It provides a peeling liquid composition for a color resist comprising 2 to 30% by weight of alkylene glycol dialkyl ether, 2 to 30% by weight of (e) water-soluble amine compound, and (f) residual amount of water.

Hereinafter, the present invention will be described in more detail.

The present invention has been conducted to effectively remove color resists and overcoats and reuse color filter substrates, which have been mostly discarded, as a result of the present invention, and it is possible to easily remove color resists and overcoats using a stripper composition having a specific composition. To discover and complete the present invention.

The (a) hydroxide compound used in the stripper composition of the present invention is selected from the group consisting of inorganic alkali hydroxides, alkyl ammonium hydroxides having alkyl groups having 1 to 4 carbon atoms, and phenylalkyl ammonium hydroxides. It is preferable. The color filter process is not significantly affected by residual metals, so inorganic alkali hydroxides can also be used. The content of the hydroxide compound is preferably 1 to 50% by weight based on the total composition, when the content is less than 1% by weight, it is difficult to completely remove the color resist due to poor penetration into the polymer component constituting the color resist. If the content exceeds 50% by weight, only the swelling phenomenon is severe, and the inorganic alkali metal precipitates, thereby changing the composition of the chemical solution, and in a certain composition, layer separation occurs, adversely affecting performance. In addition, since alkyl ammonium hydroxide and alkylallyl ammonium hydroxide are not stable, it is preferable to use it in the state dissolved in water.

The inorganic alkali hydroxide of (a) is preferably selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide and mixtures thereof. The alkyl ammonium hydroxide having an alkyl group having 1 to 4 carbon atoms is preferably selected from the group consisting of tetraethyl ammonium hydroxide, tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, and mixtures thereof. Moreover, it is preferable to use the benzyl trimethyl ammonium hydroxide as said phenylalkyl ammonium hydroxide.

In addition, the sulfur compound having the polarity (b) used in the present invention is excellent in the penetration and dissolving power to the color resist to penetrate between the polymer of the color resist causing swelling phenomenon. The amount of the sulfur compound having a polarity is preferably 5 to 30% by weight based on the total composition, when the content is less than 5% by weight, it is difficult to completely remove the color resist, and when it exceeds 30% by weight, the inorganic alkali hydroxide compound It is not expected to improve performance due to reduced miscibility with. The polar sulfur compound used in the present invention is preferably used selected from the group consisting of dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, sulfolane and mixtures thereof.

The alkylene glycol ether having an alkyl group having 1 to 4 carbon atoms (c) is excellent in the ability to lower the solubility and surface tension of the color resist to reduce the surface tension acting between the floating color resist and the glass surface easily color resist And strip, and also dissolve the binder or polymer of the stripped color resist. The amount of the alkylene glycol ether is preferably 5 to 35% by weight based on the total composition, wherein if the content is less than 5% by weight, it is difficult to completely remove the color resist, and when it exceeds 35% by weight of the inorganic alkali metal ion Performance is not expected to be impaired. The alkylene glycol ether used in the present invention is ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, Preference is given to using those selected from the group consisting of ethylene glycol monoethyl glycol and mixtures thereof.

(D) The alkylene glycol dialkyl ether having an alkyl group having 1 to 4 carbon atoms is excellent in dissolving ability to the color resist to penetrate the polymer chain of the color resist to break and release the chain so that the color resist can be easily stripped, It also functions to dissolve the binder or polymer of the stripped color resist. The amount of the alkylene glycol dialkyl ether used is preferably 2 to 30% by weight, more preferably 5 to 30% by weight based on the total composition. At this time, if the content is less than 2% by weight, it is difficult to completely remove the color resist, and if the content exceeds 30% by weight, the activity of the inorganic alkali metal ion is inhibited and performance improvement is not expected. The alkylene glycol dialkyl ethers used in the present invention are ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and these Preference is given to using those selected from the group consisting of mixtures of

The water-soluble amine compound (e) penetrates into the polymer constituting the color resist and functions to separate the color resist from the glass substrate. The content of the water-soluble amine compound is preferably 2 to 30% by weight, more preferably 5 to 30% by weight based on the total composition. If the content of the water-soluble amine compound is less than 2% by weight, the penetrating power to the color resist is weakened, so that the color resist is not completely removed and inorganic alkali hydroxide and layer separation occur. There is a problem that does not improve the performance by inhibiting the activity of the ion. It is preferable to use the water-soluble amine compound selected from the group consisting of n-methylmethanolamine, monomethanolamine, ethylenediamine and hydroxyl amine.

The water (f) used in the present invention is preferably pure water filtered through an ion exchange resin, and more preferably, ultrapure water having a specific resistance of 18 (MΩ) or more. The amount of water used may be included as a residual amount of the stripping solution composition, preferably 4 to 49% by weight based on the total composition. At this time, when the content of water is less than 4% by weight, the composition of the composition is changed at the process temperature, and inorganic alkali ions are precipitated, which causes a problem of lowering the pot life of the peeling liquid composition for the color filter. If exceeded, there is a problem that the loss of the peeling liquid composition for the color filter increases due to the evaporation of water at the process temperature.

As described above, the release liquid composition of the present invention can easily remove the color resist and the overcoat as compared with the conventional one, and can minimize the corrosion of the metal wiring under the color resist removal process.

Hereinafter, the present invention will be described in more detail with reference to the following examples. It is to be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

In the following examples, unless stated otherwise, percentages and mixing ratios are by weight.

[Example 1-12 and Comparative Example 1-22]

The contents of components (a) to (f) were mixed at the ratios shown in Tables 1 and 2, respectively, to prepare color resist stripper compositions of Examples 1-12 and Comparative Examples 1 to 22, respectively.

[Table 1]

room
city
Yes Color resist stripper composition (% by weight) (a) hydroxide
compound (b)
Sulfur compounds with polarity (c)
Alkylene glycol ether (d) alkylene glycol dialkyl ethers (e)
Water soluble amine compounds (f) water One NaOH One Sulforane 30 EG 35 Diethylene glycol diethyl ether 2 nMEA 2 30 2 NaOH 25 Sulforane 5 EG 5 Diethylene glycol diethyl ether 2 nMEA 30 33 3 NaOH 50 Sulforane 5 EG 5 Diethylene glycol diethyl ether 2 nMEA 2 36 4 NaOH One Sulforane 5 EG 35 Diethylene glycol diethyl ether 30 nMEA 2 27 5 KOH One DMSO 30 Ethylene Glycol Monomethyl Ether 35 Diethylene glycol dimethyl ether 2 MEA 2 30 6 KOH 25 DMSO 5 Ethylene Glycol Monomethyl Ether 5 Diethylene glycol dimethyl ether 2 MEA 30 33 7 KOH 50 DMSO 5 Ethylene Glycol Monomethyl Ether 5 Diethylene glycol dimethyl ether 2 MEA 2 36 8 KOH One DMSO 5 Ethylene Glycol Monomethyl Ether 35 Diethylene glycol dimethyl ether 30 MEA 2 27 9 NaOH One DESO 30 Ethylene Glycol Monobutyl Ether 5 Dipropylene glycol dimethyl ether 2 MEA 30 32 10 NaOH 25 DESO 5 Ethylene Glycol Monobutyl Ether 5 Dipropylene glycol dimethyl ether 2 MEA 30 33 11 NaOH One DESO 5 Ethylene Glycol Monobutyl Ether 5 Dipropylene glycol dimethyl ether 30 MEA 30 29 12 KOH One DESO 5 Ethylene Glycol Monobutyl Ether 35 Dipropylene glycol dimethyl ether 2 HDA 30 27

[Table 2]

(Note) In Tables 1 and 2 above,

EG: ethylene glycol

nMEA: n-methylethanolamine

DMSO: dimethylsulfoxide

MEA: Monoethanolamine

DESO: diethyl sulfoxide

HDA: hydroxylamine

[Experimental Example]

The performance evaluation of the color resist stripper composition prepared in Example 1-12 and Comparative Example 1-22 was carried out as follows using the color filter substrate of the following process.

color Resist  Removal test

Specimen Manufacturing

Color filter patterns were made on LCD corning glass with Cr / CrOx deposited on the bottom, and color resist was applied using the following photo process in the order of red, green, and blue. A universally used color resist composition (trade name: DCR-725S available from Dongjin Semichem Co., Ltd.) was spin coated to apply a final film thickness of 1.7 μm. Subsequently, the resist film was pre-baked on a hot plate at 90 DEG C for 120 seconds. Subsequently, after exposing and developing for 60 seconds at room temperature with 1% potassium hydroxide (KOH) developer, the specimen in which the said pattern was formed was hard-baked for 20 minutes at 220 degreeC.

color Resist  Removal test

The prepared specimen was immersed in a stripper composition for removing color resist at a temperature of 50 ° C. for 2 minutes, 5 minutes, and 10 minutes, respectively. Subsequently, the specimen was removed from the color resist stripper composition, washed with ultrapure water and dried with nitrogen gas, and then inspected with a scanning electron microscope (SEM; Hitachi, model name S-4100) to see if the color resist remained in the pattern. The color resist removal performance was evaluated based on the following criteria and the results are shown in Table 3 below.

◎: When all are removed completely.

○: 70% removed.

(Triangle | delta): When removed 30%.

×: not all removed

[Table 3]

Immersion time 2 minutes 5 minutes 10 minutes Example One ○ ◎ ◎ 2 ○ ◎ ◎ 3 ○ ◎ ◎ 4 ○ ◎ ◎ 5 ○ ◎ ◎ 6 ○ ◎ ◎ 7 ○ ◎ ◎ 8 ○ ◎ ◎ 9 ○ ◎ ◎ 10 ○ ◎ ◎ 11 ○ ◎ ◎ 12 ○ ◎ ◎ Comparative Example One × ○ ◎ 2 × ○ ◎ 3 × ○ ◎ 4 × ○ ◎ 5 × ○ ◎ 6 × ○ ◎ 7 × △ ○ 8 × △ ○ 9 × △ ○ 10 × △ ○ 11 × △ ○ 12 × △ ○ 13 × ○ ◎ 14 × ○ ◎ 15 × ○ ◎ 16 × ○ ◎ 17 × ○ ◎ 18 × ○ ◎ 19 × ○ ◎ 20 × ○ ◎ 21 × ○ ◎ 22 × ○ ◎

As can be seen in Table 3, Examples 1 to 12 are excellent in red, green, and blue pattern removal rate even in the initial immersion and completely removed after 5 minutes, whereas Comparative Examples 1 to 22 are initially red, The green and blue patterns were not removed at all, and after 5 minutes, some patterns remained. All patterns were removed only after a longer time.

As described above, the color resist stripper composition according to the present invention can easily remove the color resist in a short time, and in the subsequent rinsing step, water is not required to use organic solvents such as isopropyl alcohol and dimethyl sulfoxide. There is an advantage that can be rinsed only.

Claims (7)

(a) 1 to 50% by weight of a hydroxide compound selected from the group consisting of inorganic alkali hydroxides, alkyl ammonium hydroxides having alkyl groups of 1 to 4 carbon atoms and phenylalkyl ammonium hydroxides, (b) 5 to 30% by weight of sulfur compound having polarity, (c) 5 to 35% by weight of alkylene glycol ether having an alkyl group having 1 to 4 carbon atoms, (d) 2 to 30% by weight of alkylene glycol dialkyl ether having an alkyl group having 1 to 4 carbon atoms, (e) 2 to 30 weight percent of a water soluble amine compound, and (f) contains residual water, Alkylene glycol ethers having an alkyl group having 1 to 4 carbon atoms include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol Monomethyl ether, ethylene glycol monoethyl glycol and a peeling liquid composition for a color resist, characterized in that it is selected from the group consisting of these. The peeling liquid composition for a color filter according to claim 1, wherein the sulfur compound having polarity is selected from the group consisting of dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, sulfolane and mixtures thereof. The method of claim 1, wherein the alkylene glycol dialkyl ether having an alkyl group having 1 to 4 carbon atoms is ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol Color resist stripper composition, characterized in that it is selected from the group consisting of dimethyl ether, diethylene glycol methyl ethyl ether and mixtures thereof. The color resist stripper composition according to claim 1, wherein the inorganic alkali hydroxide is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, and mixtures thereof. The method of claim 1, wherein the alkyl ammonium hydroxide having an alkyl group having 1 to 4 carbon atoms is tetraethyl ammonium hydroxide, tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethylbenzyl ammonium hydroxide, and Color resist stripper composition, characterized in that selected from the group consisting of a mixture thereof. delete The color resist stripper composition according to claim 1, wherein the water-soluble amine compound is selected from the group consisting of n-methylmethanolamine, monomethanolamine, ethylenediamine and hydroxyl amine.